Preparation of a calcium and magnesium ion sequestrant

ABSTRACT

THE ELIMINATION OF PHOSPHORUS-CONTAINING COMPOUNDS FROM DETERGENT DORMULATIONS. WHICH CAUSE WATER POLLUTION, AND THEIR REPLACEMENT WITH NON-PHOSPHORUS-CONTAINING COMPOUNDS OF EQULA EFFICACY IS ACHIEVED BY EMPLOYING THE CURED PRODUCT OF THE REACTION BETWEEN 6-CARBOXY CELLULOSE AND AN AQUEOUS SOLUTION OF A LEWIS ACID CATALYST.

United States Patent US. Cl. 260-212 Claims ABSTRACT OF THE DISCLOSURE The elimination of phosphorus-containing compounds from detergent formulations, which cause water pollution, and their replacement with non-phosphorus-containing compounds of equal efiicacy is achieved by employing the cured product of the reaction between 6-carboxy cellulose and an aqueous solution of a Lewis acid catalyst.

This is a division of application Ser. No. 157,616, filed June 28, 1971, which issued June 19, 1973 as US. Pat. No. 3,740,339.

The present invention relates to a product which can be used in a detergent formulation to replace sodium tripolyphosphate. More particularly, it relates to a nonphosphorus-containing composition, and the process of its manufacture, as a calcium and magnesium ion sequestrant in a detergent formulation.

Modern detergents are intimate mixtures of several components including a surfactant, a soil suspension agent, a calcium and magnesium ion sequestering agent and, optionally, inorganic salts as fillers, optical brighteners and bleach crystals. The surfactant usually is an alkyl or alkylaryl sulfonate, though other anionic, nonionic or cationic surfactants may be used. Carboxymethyl cellulose is the soil suspending agent in most detergents. Sodium tripolyphosphate is the calcium and magnesium ion sequestering material. It also serves as a buffer insuring a moderately alkaline pH for optimum detergency. Sodium silicate is the most common optional filler and, because it inhibits corrosion of Washing machines, its use is becoming general in detergents.

Replacement of sodium tripolyphosphate is necessary because of ecological considerations. Phosphorus is an essential nutrient for living organisms along with nitrogen and carbon. Polyphosphate in efiluent waters is converted by hydrolysis to phosphate ion. Phosphate ion is an eflicient source of nutrient phosphorus. If the eflluent water contains a biological excess of carbon and nitrogen, phosphorus becomes the controlling element for microorganism growth. Where the concentration of all three elements is high, algae growth occurs rapidly and the waters become fouled by a green scum. This has occurred to many lakes in developed regions throughout the world.

How often phosphorus is the growth controlling element is questionable, although cases have been documented where it is and lake fouling has occurred. Up to 60% of this phosphorus comes from detergent polyphosphate; the remainder comes from fertilizers and other sources. Thus it is desirable that phosphorus should be eliminated from detergents.

Natural hard waters contain large amounts of dissolved carbon dioxide. At the alkaline pH values necessary for dctergency, calcium and magnesium carbonate will precipitate. These precipitates lead to greying of white fabrics. Detergency is also harmed by their presence and so a means of keeping calcium and magnesium ions in solution is required. The ability of the ions to adversely interact with the surface" active detergent component must also be destroyed.

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Precipitation of calcium and magnesium carbonate does not occur in the presence of sodium tripolyphosphate. This can be demonstrated by adding a mixture of sodium carbonate and sodium tripolyphosphate to a synthetic source of hard water such as is described in US. Federal Specification P-D-245a. The magnesium and calcium carbonate precipitate does not form. Sodium tripolyphosphate also prevents the adverse action of calcium and magnesium ion on the surface active component and it supplies the alkalinity necessary for good detergency.

Prevention of the precipitation of carbonates by sodium tripolyphosphate and the elimination of the adverse effect of calcium and magnesium ions on detergency is known to be due to the chelating action of sodium tripolyphos phate. In simplest terms, this means the calcium and mag nesium ions are surrounded and rendered incapable of forming insoluble carbonates or of harming detergent action by the tripolyphosphate molecule in the form of a claw.

Accordingly, it is an object of the present invention to provide a sequestrant which does not contain phosphorus and a process for the manufacture of said sequestrant.

It is another object of the present invention to provide a washing composition which is free of phosphorus-containing compounds, but which possesses the advantages of polyphosphate compounds.

It is yet another object of the present invention to provide a non-phosphorus-containing compound whose sequestering activity is non-permanent and which decomposes quickly after completion of washing.

Additional objects will become apparent from a consideration of the following detailed description of the invention.

It has been found in accordance with the present invention that a phosphorus-containing sequestrant, particularly sodium tripolyphosphate, can be completely eliminated from detergent systems and results comparable to those attained by using a polyphosphate are achieved by utilizing as a sequestrant the heat cured reaction product of 6-carboxy cellulose and an aqueous solution of a Lewis acid catalyst in a detergent washing system.

6-carboxy cellulose itself, which has not been treated in accordance with the present invention, has been recognized as a soil suspending agent useful in detergents. However, it cannot sequester calcium or magnesium. This can be readily demonstrated by the addition of sodium carbonate and 6-carboxy cellulose to water-containing magnesium and calcium ion. A convenient synthetic source of such water is the 300 p.p.m. synthetic hard water described in US. Federal Specification P-D-245a. When carbonate ion is added to this Water, a white or grey cloudy precipitate forms in a minute or two. If 6-carboxy cellulose is present and sufllcient sodium carbonate is added to maintain alkaline pH values, above pH 8.5 or 9.0, the 6-carboxy cellulose will dissolve and the cloudy precipitate will still form. The precipitate can be isolated by centrifugation and identified as a mixture of calcium and magnesium carbonates by conventional means.

However, it has been found that the Lewis acid treated 6-carboxy cellulose after heat curing, which is the product of the present invention, prevents precipitate formation for periods of time which are suflicient to complete the washing cycle.

The 6-carboxy cellulose used in this invention is conveniently produced by nitrogen dioxide oxidation of cellulose. This process is well known and carried out by whatever means is convenient and economic. Thus, gaseous or liquid N0 can be used and a solvent is optional. The choice of the cellulose starting material is also dictated by convenience. Cotton, cotton linters, regenerated cellulose or wood pulp may be used. Because of economic factors, bleached wood pulp is preferred.

The oxidation of cellulose by nitrogen dioxide can be interrupted at any stage to give a product containing almost no carboxyl to one containing 25.6% carboxyl. Each C carbon atom is in the form of a carboxyl group when 25.6% carboxyl is present. Carboxyl is conveniently measured by the calcium acetate method developed by Yackel and Kenyon, Journal of the American Chemical Soc., 1942, 64, 121-427. This method is not strictly accu rate at the highest carboxyl levels. At these levels it measures calcium ion accessibility, which is an excellent practical result for present purposes.

The carboxyl content of the 6-carboxy cellulose used in accordance with the present invention can be from about 12% to about 25.6%, with from about 19% to 25.6% being preferred. As carboxyl ion is involved in the calcium and magnesium sequestering process, the higher the carboxyl level the better the results achieved and, therefore, the use of a 6-carboxyl cellulose having a 25.6% carboxyl content is especially preferred.

While oxidation with nitrogen dioxide is referred to, it should be noted that any related method giving predominate attack at the C position on the anhydroglucose unit is not excluded for preparation of 6-carbo-xy cellulose. An example of such a process is oxidation of cellulose by a mixture of nitric acid and sodium nitrite.

The Lewis acid used as a catalyst for converting the 6- car-boxy cellulose into a calcium and magnesium sequestering or chelating agent can be selected from the group consisting of hydrated and unhydrated magnesium salts of mineral acids, aluminum salts of mineral acids, acetic acid, zinc salts of mineral acids, boron trifluoride and zinc fluoborate. It is preferred to employ either magnesium chloride or magnesium nitrate. Magnesium nitrate is especially preferred because after it reacts with the 6-carboxy cellulose and is heat cured, the cured 6-carboxy cellulose is less highly colored in solution than when magnesium chloride is used.

In preparing the sequestrant of the present invention, 6-carboxy cellulose is soaked in an aqueous Lewis acid catalyst solution. The time of soaking or steeping is immaterial, provided that suflicient time is available to thoroughly and uniformly wet out and contact the 6- carboxy cellulose with the catalyst solution. The concentration of 6-carboxy cellulose is also immaterial, provided again that it is not so high that uniform Wetting and contact with catalyst is impossible. Thus, with highly efiicient mixing equipmen 50% or more 6-carboxy cellulose can be used. At this level filtration of excess buifer solution would be unnecessary. The lower limit for 6-carboxy cellulose concentration is set simply by convenience. Too little 6-carboxy cellulose requires mixing large volumes of catalyst solution and filtration of these large volumes at the end of steeping. About 4% of 6-carboxy cellulose is preferred, since this amount does not require excessive volumes of catalyst solution, is easy to disperse and thoroughly wet out, and the excess is readily filtered.

The concentration of the catalyst in the steeping solution can be from about 0.1% to about 60.0%, by weight, preferably from about 1.0% to about 20.0%. Desirably, however, the catalyst concentration, especially when magnesium salts of mineral acids are being used, should be kept as low as possible in the steeping solution. This is simply because the magnesium ion from the catalyst must be sequestered, thus leaving a reduced amount of sequestering capacity for removing the calcium and magnesium ions from hard water and from soil. Accordingly, it is especially preferred to employ about 4%, by weight, of the catalyst in a steeping solution containing 4%, by Weight, of -6-carboxy cellulose, resulting in a 1:1 ratio of catalyst to 6-carboxy cellulose in said steeping solution.

The time of cure is directly related to the efliciency of heating. Accordingly, the cure temperature can be anywhere from 100 C. to about 200 C. and the curing time can be anywhere from one minute to about 24 hours. A y g ime should be avoided, if possible, as an excessively colored product is obtained. It is preferred to cure at a temperature of from about C. to about 160 C. with a temperature of C. being especially preferred. When cure is effected at a temperature of from about 140 C. to about (3., when employing 4.0% of magnesium nitrate in a steeping solution containing 4.0% of 6-carboxy cellulose, it is preferred'to cure for from about 10 minutes to about 20 minutes, with 15 minutes being especially preferred. When curing at 140 C. and above for periods in excess of one hour a highly colored product is obtained, which would, when employed in a detergent formulation, blacken the wash water. When low cure temperatures are employed much longer times for effecting cure are necessary, even as much as 24 hours if the concentration of the catalyst is low or if it is entirely absent. It has been noted that even in the absence of a Lewis acid catalyst a small amount of calcium sequestering ability is observed after curing the '6-carboXy cellulose for 16 hours at 105 C. It has also been noted that sequestering ability is not developed at 150 C. in the absence of a catalyst; decomposition and an unacceptable color occur instead.

After steeping, the excess catalyst solution is removed by filtration, centrifugation or any other convenient means, and the 6-carboxy cellulose containing the physically adsorbed catalyst can, optionally, be dried, or directly cured in the wet state with provision for the removal of water vapor. When cured from the wet state, the time necessary for effecting cure increases. If drying is used prior to curing, this can be done at about 105 C.

for a period of from about 30 to about 45 minutes in a forced draft oven.

Thhe cured 6-carboxy cellulose is converted into a powder by grinding. To provide a detergent composition of suitable alkalinity and buffering capacity, the cured 6- carboxy cellulose is mixed with an alkaline salt or salts, to give a 1% solution of the detergent composition a pH of from about 7.0 to about 11.5, preferably from about 9.0 to about 10.6. Exemplary of the alkaline salts which can be used are: sodium silicate, sodium sesquicarbonate, sodium carbonate, potassium silicate, potassium carbonate, sodium borate, sodium acetate and mixtures thereof. The alkaline salt or mixtures thereof can constitute from about 30% to about 75% of the detergent composition.

The surfactant or surface active agent employed in the detergent composition can be anionic, cationic, nonionic, ampholytic, zwitterionic, or any suitable mixture of two or more of these. The ratio of surfactant to the mixture of cured 6-carboxy cellulose and the alkaline salt(s), which together can be considered to form a detergent builder, can be from about 1:10 to about 3:1, by Weight.

In addition, carboxymethyl cellulose, which is a soil suspending agent, fillers, optical brighteners, etc., can be added.

EXAMPLE 1 In this example, 6-carboxy cellulose of 21.4% carboxyl content was stirred with various catalyst solutions, filtered, dried at 105 C. in a forced draft oven and cured for 15 minutes, also in a forced draft oven. The cured products were powdered in a Wiley mill and 0.96 g. of the resulting powder was mixed with 2.17 g. of sodium carbonate. The mixtures were stirred for 20 minutes in 200 mls. of the 300 p.p.m. hardness water described in U.S. Federal Specification PD245a. Two water temperatures were used, 65 C. and 25 C. After stirring, solids were removed by centrifugation and washed two times with 50 g. portions of distilled water to remove traces of sodium carbonate. After decanting the last wash, the precipitates were treated with concentrated hydrochloric acid and the gas evolution observed. This distinguishes between precipitated carbonates and any residual insoluble 6-carboxy cellulose.

TABLE I The mixed carbonates precipitation test outlined in Ex- Pemest m. ample 1 was used to compare the sequestrant of the prescmlysim Cum Test 1mm Gas ent invention, cured 6-carboxy cellulose, wlth other sesteeping temp. temp. hard evolu- Catalyst type solution 0.) 0.) water tlon q 6%??8 it? 113 2?. 5 TABLE III A etl ar-iii-.- 140 65 T Gas Pptd. Do 10 140 25 est i 10 120 65 Weig ht temp. during lustand- D0 10 120 25 Sequcstermg agent ((1.) 0.) test tron ing $18}; 8 58 S; i i 10 Gluconic acid 0.06 65 NHiN a. 10 120 65 P-: 25

NHJNOL 10 120 5 C1tr1ca01d 0.96 65 NH4NO 1 140 65 25 NHiNoa-n 1 25 22 1 r CMSCN) 3 120 65 Do 0: 2 5 +1 Sodium trip0lyph0sphate.. 0.96 26 & 65

The results in Table I illustrate the good behavior re- 3 8% 32 g 2 sulting from use of the magnesium chloride catalyst com- Cured gj g i 'ggflgflfii 24 25 65 "5"" pared to the other catalysts tried. Acetic acid sequestered 3g g g? a the hard water ions only at 25 C. Calcium thiocyanate was tried since it is known to strongly decrystallize cellut. 2 Halelose. It was unsuccessful. Decrystallization involves a loss Obviously the ssquestrant of the Present invention is a of order m the arrang"jment In space of the 6ca rboxy more efficient sequestering agent for Mg++ and Ca++ ions cellulose molecules- Thls could, Cause F f faclle re in hard water than gluconic, citric or diglycollic acids, arrangement of the molecules into their act1ve, calcium and is equally as good a sequestrant as sodium triPolysequestenng formphosphate or nitrilo triacetate, which increases pollution EXAMPLE 2 in waters where nitrogen is the growth controlling ele- 'ment.

The efi'ects of variables in production of the sequestering EXAMPLE 4 material are given next, using absence of precipitation and absence of gas evolution as a criterion for the ability to A cured, powdered 6-carboxy cellulose having a carsequester. The 300 p.p.m. hard water was the same as that boxyl content of 21.4%, as measured by the calcium aceused in Example 1. Tests for precipitation and carbon ditate procedure of Yackel and Kenyon, J.A.C.S., 1942, oxide evolution were also carried out as in Example 1. vol. 64, pps. 121-127, was prepared by steeping the 6- The non-permanent nature of the sequestrant is illustrated carboxy cellulose in an aqueous solution containing 4% by precipitate formation on standing. When a precipitate Mg(NO .6I-I O until the -carboxy cellulose was wetted formed on standing, it always liberated CO gas after cenout, and was then cured for 15 minutes at 150 C. in a trifugation, washing and treatment with concentrated hyforced draft oven. The product was then used in comdrochloric acid. Sufiicient Na CO was added in each case pounding detergent formulations. In each experiment the to give a pH of 10.2-10.4 to the hard water. organic surfactant in the detergent formualtion was a so- TABLE II Percent Grams Mg(NO5)i- Cure cured Test Pptd 61120 Temp. Cure time G-carboxy temp. during Gas Pptd. on insteep 0.) (min.) cellulose 0. st evolution standing a 15 0. 96 25 3 120 15 0.48 25 3 120 15 0.24 25 a 120 15 0.12 25 a 120 15 0.96 65 3 120 10-20 0. 48 65 3 120 15 0. 96 25 2 15 0.48 65 4 150 15 0. 48 65 3 15 0.48 65 4 160 15 0.48 65 4 150 15 0.24 65 4 150 15 0.12 65 Haze 4 150 15 0.12 25 This table illustrates the excellent sequestering power dium linear alkylate sulfonate. The formulations were found at a hard water temperature of 25 C. in almost compared with a tripolyphosphate-containing formulation every case. sequestering in 65 C. water is more difficult. for their soil removal ability.

4% catalyst and high cure temperature is required for 69 Standard soiled white cotton cloth (U.S. Testing Corngood 65 C. sequestering ability. pany) was used in all tests. The total color diflerences AB The concentration of the sequestrant of the present inbetween the cloth and a white ceramic standard was measvention which would be used in a home washing machine ured before and after laundering. Results are expressed lies between the 0.12 g. and the 0.24 g. levels in Table II as the difference in total color before and after laundering. above. In a hot water wash, where the water temperature 65 A Hunter color difference meter, Model D25, was would rarely be higher than 65 C., or times longer than used with the white ceramic standard. Measurements 20 minutes, a 150 C., 15 minute cure is optimum. were made to determine the lightness L of the cloth and,

in addition, the red and green color factor a and the EXAMPLE 3 yellowness or blueness factor b were determined. The 70 total color difference from the white standard was calcu- 111 the eXpenmellts 11Sted below 111 Table n the cured lated for both sides of each cloth sample by the equation: 6-carboxy cellulose, in each instance, contained 21.4% 2 2 2 carboxyl, it was steeped in an aqueous solution containing 1+ 4% of Mg(NO .6H O, and was cured at 150 C. for 15 AL is the difference in lightness between the white ceramic minutes. 75 standard and the sample.

Aa is the difference in the red and green color factor between the white ceramic standard and the sample. Ab is the difference in the yellow and blue color factor between the white ceramic standard and the control.

8 ture in the 150 p.p.m. hard water. The sequestering material, surfactant, laundering test procedure and measuremerit of AC, the color dilierence due to laundering, were identical to those used in Example 4.

TABLE V [Detergent formulation in percent by wt] Sodium Carboxy- Cured 6- Sodium silicate Grams Color methyl carboxy tripolypenta- Sodium Sodium mixture pH after difference Surfactant cellulose cellulose phosphate hydrate sulfate carbonate used washing (AC) Then the loss in total color difference AC caused by laundering of one side of the cloth sample is found from the equation:

where A D and AB are the color difierences between the cloth and the white ceramic standard before and after laundering respectively. As the cotton cloth was white before soiling, AC is a measure of the soil removed. The values for each side were averaged and results given as averages for the two sides of each sample.

After preparation and blending of the detergent mixtures, 0.30 g. of each was added to 200 ml. portions of 65 C., 150 p.p.m. synthetic hard water in Launder-Ometer jars. The 150 p.p.m. water was prepared simply by diluting the water used in Examples 1 to 3 with an equal volume of distilled water. The Launder-Ometer jars contained 100, A" diameter steel balls. The jars were rotated in the Launder-Omcter at 65 C. for 10 minutes, the supernatent liquid drained off and two rinses with 150 p.p.m. water (200 ml.) was carried out. Three minutes were required for each rinse. Then a fresh 0.30 g. of detergent and fresh 150 p.p.m. hard water was added and the wash cycle and two rinses were repeated. After a third wash with a third 0.30 g. detergent mixture followed by the two rinses, always with 65 C., 150 p.p.m. hard water, the cloths were squeezed to remove as much water as possible, blotted on pulp sheets and dried in a 105 C. forced draft oven for minutes. AC, the color difference due to laundering, measures soil removal. The higher the value of AC, the better is the soil removal.

In these tests, cured 6-carboxy cellulose was distinctly better than sodium tripolyphosphate when 0.250 g. of detergent mixture was used in the test. As 200 ml. of water are used in each laundering stage, 0.250 g. detergent mixture corresponds to 0.125% detergent in the wash. This is close to 0.12-0.18%, the' amounts often recommended by detergent manufacturers for home laundry use for tripolyphosphate-containing detergents.

What is claimed is:

1. A process for the production of a calcium and magnesium ion sequestrant for use in a detergent composition which comprises the steps of:

(a) reacting 6-carboxycellulose having a carboxyl content of from about 12% to about 25.6%, by weight, with from about 0.1% to about 60.0%, by weight, of an aqueous Lewis acid catalyst solution, said Lewis acid catalyst being selected from the group consisting of hydrated and unhydrated magnesium salts of mineral acids, aluminum salts of mineral acids, acetic acid, zinc salts of mineral acids; boron trifluoride and zinc fluoborate;

(b) curing the product of step (a) at a temperature of from about 100 C. to about 200 C. for a period of from about 1 minute to about 24 hours.

2. The process of claim 1 wherein said 6-carboxy cellulose has a carboxyl content of 25.6%.

3. The process of claim 1 wherein said Lewis acid is selected from the group consisting of magnesium nitrate and magnesium chloride.

TABLE IV [Detergent formulation in percent by wt.]

Sodium Carbexy- Cured 6- Sqdium silicate Grams Color methyl earboxy tnpolypenta- Sodium Sodium mixture pH alter difference Surfactant cellulose cellulose phosphate hydrate sulfate carbonate used washing (AC) It is evident from the above results that the cured 6- carboxy cellulose of the present invention removes soil at least as well as sodium tripolyphosphate.

EXAMPLE 5 In this example, additional soil removal test results are given. Less sodium silicate was used in these test formulations than in those outlined in Example 4. 'Results are given for tests run using 0.125 and 0.25% detergent mix- (References on following page) 9 10 References Cited 3,215,488 11/1965 Suiter 260-212 3,372,979 3/1968 Reinhardt et a1 260-212 UNITED STATES PATENTS 3,551,410 12/1970 MacDonald et a1. 260-212 1,576,631 3/1926 Defaucamberge 260-212 1,771,460 7/1930 Lilienfeld 260212 5 DONALD E. CZAJA, Primary Examiner 2,448,892 9/1948 Kenyon et a1. 260212 R I FIN A 2,589,190 3/1952 Hanson 252 130 SslsantEXammer 2,758,112 8/1956 Waning 260212 U.S.C1.X.R. 3,111,513 11/1963 Battista et a1 260212 260231A 3,173,751 3/1965 Daul et a1 260212 10 

